CN1234801C - Liquid crystal mixture and liquid crystal unit and use of dye having dipole for mixture - Google Patents
Liquid crystal mixture and liquid crystal unit and use of dye having dipole for mixture Download PDFInfo
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- CN1234801C CN1234801C CNB011354046A CN01135404A CN1234801C CN 1234801 C CN1234801 C CN 1234801C CN B011354046 A CNB011354046 A CN B011354046A CN 01135404 A CN01135404 A CN 01135404A CN 1234801 C CN1234801 C CN 1234801C
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
- G02F1/13725—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering based on guest-host interaction
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0488—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a special bonding
- C09K2019/0496—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a special bonding the special bonding being a specific pi-conjugated group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/031—Polarizer or dye
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/01—Materials and properties dipole
Abstract
The present invention relates to a liquid crystal mixture, especially for a liquid crystal cell for a color liquid crystal display (LCD), comprising a liquid crystal material and a dye, wherein said dye has a dipole, preferably a permanent dipole. The invention further relates to a liquid crystal cell for a color liquid crystal display comprising a liquid crystal mixture, substrate plates or substrate means for comprising said liquid crystal mixture, electrodes for applying an electric field to said liquid crystal mixture and a voltage source for applying a voltage to said electrodes, wherein said liquid crystal mixture comprises a dye with optical anisotropic properties having a dipole, preferably a permanent dipole. The invention further relates to a use of a dye with a dipole for a liquid crystal mixture, especially for a liquid crystal cell and/or liquid crystal displays.
Description
Technical field
The present invention relates to a kind of liquid crystal compound, a kind of application that is used for the liquid crystal cells of chromatic liquid crystal screen LCD and is used for liquid crystal compound with dipolar dyestuff.
Background technology
Liquid crystal and liquid crystal compound can have extensive use.The most general a kind of of liquid crystal applications is liquid crystal display LCD, especially to notebook computer, but also is used for fixing the display monitor central monitoring system of the desk-top computer of system more and more.
One of most important advantage of liquid crystal display is, compares with other indicating meter, and its size is little, generates picture and do not glimmer, and very convenient to the user, especially the eyes to the user have provide protection, particularly for the people who works long hours before display screen.
Liquid crystal display comprises an array liquid crystal cells.In recent years, having developed has various liquid crystal cells, and most important liquid display unit is TN unit (twisted nematic unit), STN unit (super-twist nematic unit), PDLC unit (polymer dispersed liquid crystal unit) or the like.Liquid crystal cells adopts nematic liquid crystal usually, still, also can adopt smectic liquid crystal or cholesteric liquid crystal.
All above-mentioned liquid crystal materials generally all have common trait.They provide a kind of molecular structure of rod shape, hard major axis and dipole, and/or be easy to the polar substituting group, therefore can provide permanent or inductive dipole.
Mesomorphic obvious characteristic be molecule be tending towards along equidirectional towards trend, be called as the guiding dipole (director).This being tending towards of liquid crystal molecule caused being called as anisotropic condition towards the trend along guiding dipole direction.This term refers to the performance of material, optical transmission performance especially, and this depends on the direction that they are measured.The anisotropic character of liquid crystal is to cause the major cause of its unique optical properties.
In liquid crystal cells and liquid crystal display, the directivity of molecule can be controlled by liquid crystal material or mixture or liquid crystal cells are applied the electric or magnetic field.These liquid crystal molecules have a kind of permanent dipole or induced dipole, itself are easy to be orientated along the electromagnetic field direction.
Liquid crystal compound or liquid crystal cells are applied the electric or magnetic field, general molecule can be changed between two states or two kinds of directions, and a kind of is " on-state ", and the liquid crystal cells preferred orientations is transparent this moment, with a kind of " off-state ", the preferred orientations of liquid crystal cells is opaque this moment.
Relevant with liquid crystal cells, transparence is subjected to the influence of various effects: for TN unit (twisted nematic unit), the light polarization meeting in the liquid crystal material is influenced, and provides polarisation filter in the both sides of liquid crystal material.Polarization in the liquid crystal material is subjected to unaffected, depends on to add electromagnetic field, so two polarisation filters of light transmissive above-mentioned " on-state ", or transmissive does not pass through " off-state " polarisation filter.
For PDLC unit (polymer dispersed liquid crystal unit), little liquid crystal droplet is dispersed in the transparent polymer matrix.The diameter and the visible wavelength of liquid crystal droplet are equally matched.Because droplet dia is little of thickness, as long as " off-state " following enough big of the refractive index mismatch between liquid crystal and polymkeric substance, then first direction (is main in this direction transmission for the function of liquid crystal cells or display screen promptly, therefore, being also referred to as function direction or preferred orientations) light launched can be scattered repeatedly before penetrating by film.Do not having under the situation of applied field, because above-mentioned scattering, film can be rendered as milky.On the other hand, in " on-state ", when the guiding dipole that makes single drop with a kind of field was directed, the specific refractory power of liquid crystal can become and very approach the specific refractory power of polymer matrix material in the drop, so liquid crystal material can bleach in above-mentioned preferred orientations.And when cancelling this, its inceptive direction can be recovered in the liquid crystal farmland, because the effect of surface force, because its hole is not the ideal sphere yet.The nephelometric turbidity unit of " off-state " will depend on the size and the number density of refractive index mismatch amount, liquid crystal droplet.
For the energy color information display, to add dichroic dye in the liquid crystal material.
In general, liquid crystal is best solvent to organic molecule especially.Therefore, when the dyestuff with a small amount of geometrically anisotropic was mixed in the liquid crystal, this dye molecule can join with liquid crystal anisotropic molecule interphase interaction field coupling; They tend to the mode that is orientated along liquid crystal guiding dipole direction by its molecular long axis and arrange.When applying a kind of, when preferably applying electric field, dye molecule can be changed along liquid crystal orientation.This phenomenon is called as " host and guest's interaction ", so each liquid crystal cells is called as guest-main effect unit.
Make the quality of liquid crystal cells or liquid crystal display reach good contrast on the one hand, homogeneous color, thus optical property is good, makes liquid crystal cells reach the time of response in the unit when for example off-state is changed under on-state or reverse direction on the other hand.
(rise time) is normally defined to the rise time, and liquid crystal material or unit reach and connect 90% of the required time of transmission state when applied field.Equally, to being defined as die-away time, liquid crystal material reaches and connects 10% of the needed time of transmission state when being zero in the setting field.Fast response time, especially to mobile image, and also extremely important to the application of standard computer with image change.
Summary of the invention
Therefore, the object of the invention is to be provided for a kind of liquid crystal compound and a kind of liquid crystal cells of liquid crystal display, and it can provide the speed with high response, short rise time and die-away time.
This purpose of the present invention is by according to a kind of liquid crystal compound of claim 1, realize in the application of liquid crystal compound according to a kind of liquid crystal cells that is used for chromatic liquid crystal screen (color LCD) of claim 20 with according to the dyestuff of the band permanent dipole of claim 27.Claims 2-19,21-26 and 28-35 relate to this liquid crystal material and unitary separately preferred embodiment, and relate to the application with dipolar dyestuff.
According to the present invention, this liquid crystal compound promptly is specifically designed to the liquid crystal compound of the liquid crystal cells of chromatic liquid crystal screen, comprises a kind of liquid crystal material and a kind of dyestuff, and wherein said dyestuff has dipole.This dyestuff preferably is with permanent dipole, but to some application, induced dipole is also enough.Be with dipolar dyestuff by interpolation, its rise time can significantly shorten.This is because the additional dipole of dyestuff directly is subjected to the influence of applied field, and the result is that total " orientation force " by the interaction realization of applied field and the total moment of dipole of liquid crystal compound may strengthen.On the other hand, this die-away time is but influenced hardly, especially can not increase because of the dyestuff that interpolation has a permanent dipole.
The reduction of time of response, especially rise time are important for favorable optical performance, in addition, can reduce the lower limit of display screen operating temperature,, limit the suitability of liquid crystal compound and liquid crystal cells or liquid crystal display because generally can increase with the reduction of temperature switching time.Therefore, according to liquid crystal compound of the present invention and be used for chromatic liquid crystal screen comprised that with a kind of liquid crystal cells of dipolar dyestuff both broadening it can adopt the temperature range of this liquid crystal material or mixture and unit and display screen, also provide under standard conditions better optical quality to the user.
Dyestuff on this application value, be to comprise at least one chromophoric a kind of medium or molecular cell, wherein chromophoric group has only by the wideest possible understanding and explains, promptly produces any molecular cell of colour effect, no matter is independent or in conjunction with any other molecule or atomic unit.Usually chromophoric group belongs to π-electron system.One or more chromophoric grouies all can be combined to chromogen (Chromogene), also can explain by the wideest possible explanation.
In addition, can comprise additional group according to dyestuff of the present invention, wherein these groups at least also can influence colour effect, and still, these additional groups also can be to group or the unit of dyestuff colour effect without any influence.These groups for example can belong to auxochromous group (auxochrome groups), as NR
2, OR, COOH, SO
3H or the like causes the drift of colour or color wavelength usually respectively.
Each molecular cell or subelement can combine separately or with other molecular cell or subelement, to providing dipole according to dyestuff of the present invention.Especially can provide dipole to this dyestuff by one or more chromophoric grouies and/or in chromogen unit or subelement.Also can provide dipole by the unit (or subelement) that is not included in the extension group (extensional group) in chromophoric group or the chromogen.These extension groups can influence or not influence the chromatic effect of generation of dyestuff, as mentioned above.
Especially may with preferably, by interpolation or delete cells, molecule and/or atom and/or ion, revise the existing dyestuff of travelling to and fro between intermolecular no moment of dipole, so that dyestuff produces moment of dipole.As mentioned above, this may cause color drift, and still, yet can add or delete have the unit of influence to producing colour effect, therefore can add the desired dipole of dyestuff yet.
The colour effect that should be noted that dyestuff should be preferably human eye visible colour effect, but also can be the colour effect in the human eye nonvisible wavelength scope.Therefore,, must be understood by the widest possible range colour effect when light being transmitted and/or absorption and/or reflex time with the liquid crystal compound that has according to dyestuff of the present invention,, i.e. the displacement of any optical wavelength.
Certainly, the term dyestuff also is not limited only to dye, also can comprise two or more different dyestuffs in according to liquid crystal compound of the present invention.
To the liquid crystal on the meaning of the present invention " mixture ", only be interpreted as the mixture of general meaning, comprise basically that all are available or be useful on the material or the element of functional mixture or functional layer.Therefore, be applied under the situation of the liquid crystal cells of display screen for example, having only this liquid crystal compound itself regarded as to be whole film or unit itself.It can comprise only a kind of liquid crystal material of particular type, also can comprise a kind of mixture of different liquid crystal materials.It also can comprise the other material of non-liquid crystal.In addition, the liquid crystal compound in meaning of the present invention can comprise as comprising the polymeric matrix of liquid crystal droplet, as after this explaining in conjunction with preferred embodiment.This liquid crystal also can embed in other material or the molecular radical.In addition, the interaction of any kind or chemical bonding all may occur between one or more liquid crystal materials and/or other material or group, but still are included in this term liquid crystal compound.
Have dipolar dyestuff, preferably have the dipolar dyestuff of permanent electric, play a kind of bifunctional dyestuff, not only optics having been shown provides colour but also provides moment of dipole to fast response time.In addition, this dyestuff preferably has optically anisotropic performance.
The liquid crystal material that is used for liquid crystal compound can provide induces eelctric dipole, when applied field, the small rearrangement by electronics in the molecule and proton realizes, but preferably this liquid crystal molecule has strong permanent electric dipole, reach higher total dipole and higher " orientation force " thus, as described above.Liquid crystal with ferroelectric properties is especially preferred.
The resistivity of liquid crystal material is preferably very high, so that adopt the liquid crystal cells of liquid crystal compound of the present invention or the power consumption of liquid crystal display to reduce.Resistivity is preferably greater than 10
12Ω cm is more preferably greater than 10
13Ω cm.
In a preferred embodiment, because this liquid crystal compound of twisted nematic effect (TN effect) of above explanation is can operate with controllable, wherein preferably adopt 4 '-n-pentyl-4-cyanobiphenyl liquid crystal, called after 5CB hereinafter.
In another preferred embodiment, this liquid crystal compound comprises by the liquid crystal droplet of even dispersion in a kind of transparent polymer matrix, forms a kind of liquid crystal (PDLC) of polymkeric substance disperse, and is also as discussed above.
Preferred material is a kind of liquid crystal compound, is promptly for example provided by Merck Limited (GreatBritain) company, and the trade mark is " BL001 " (formal E7), and the structure representation of BL001 is following general formula:
25％
16％
As polymer materials, the preferred photosensitive polymer that is exposed to meeting solidified clear, colorless liquid state under the UV-light that adopts.This photosensitive polymer is for example provided by Norland ProductInc. (U.S.), and its trade mark is " Norland Optical Adhsive 65 (NOA65) ".
The drop preferred size is at the 0.01-20 mu m range, more preferably between 0.5-5 μ m.The liquid crystal droplet size especially is preferably about 3 μ m.The reason that adopts this size is because very big and very little drop scattered light effectively all.Have now found that, optimum size be about 5 times to institute's optical wavelength transmission scope, therefore, approach 3 above-mentioned μ m.In a preferred embodiment, the shape of drop is spherical substantially, wherein also some ununiformity may occur.But, also may be the drop of other shape, must understand what restriction is the shape of drop do not had.
Preferred liquid crystal compound of the present invention is used for can operating and controllable liquid crystal cells according to guest-main principle, as mentioned above.
For the time of response is significantly reduced, especially the rise time significantly reduces, and the dyestuff of liquid crystal compound of the present invention will have the permanent dipole that surpasses 5 debye, preferably surpasses 10 debye, most preferably more than or equal to 15 debye.Certainly, the present invention also can adopt and have higher dipolar dyestuff.
Preferred this liquid crystal compound order parameter (order parameter) is more than 0.5, more preferably more than 0.7.This order parameter is a parameter that the preface of mixture is provided quantitative measure.Order parameter S is defined as follows:
A wherein
|And A
⊥Be to the unit disconnect respectively with on-state under the absorbance determination value.
Dyestuff preferably has high solubleness in liquid crystal compound of the present invention, preferably more than 0.5 weight %, more preferably more than 1 weight %.
This liquid crystal material preferably contains the dyestuff of one of not enough percentage to about 5 weight %, preferably between 0.5-2 weight %, most preferably at about 1-1.5 weight %.This weight % be according to all liquid crystal compounds comprise might measure by composition, also may comprise non-liquid crystal group or or unit or material, even comprise this dyestuff.
To the most preferred dyestuff of liquid crystal compound of the present invention is to have C
22H
28N
4The Morpip that O forms.The chemical formula structure of Morpip is as follows:
The moment of dipole of Morpip in chloroform is 15 ± 1 debye (depending on polarity of solvent), in 454.5 nanometers absorption peak arranged, and therefore is suitable for most liquid crystal compound of the present invention.
The suitable general formula of preferred coloring agent is expressed as follows:
Wherein " D " represents electron donor's group, and " π " pi-conjugated system of expression and " A " expression electronics are subjected to main group.Electron donor's examples of groups comprises dialkyl amido, pyrido, Mi Dingbing or the like.Electronics is subjected to main examples of groups to comprise nitro, dicyano methanides (dicyanomethanide), tricyanomethanides (tricyanomethanide) or the like.The example of π system comprises all conjugated systems, and can comprise thiphene ring unit and phenyl unit and vinyl units.As the example of general type, comprise the dyestuff of all following two general formulas:
Wherein D and D ' represent suitable electron donor's group, and Y represents hydrogen or halogen.If halogen, Y fluorine preferably then.
Other example that moment of dipole is higher than the molecule of 10D is known.Another example is as follows, and the moment of dipole of following dyestuff is 17D.
The dichroic ratio that this liquid crystal compound preferably provides is at least 2, and more preferably at least 5, most preferably at least 7, so that higher.By the function direction detection, this dichroic ratio is defined as this liquid crystal compound or unit and connects ratio to transmitted intensity under the off-state.High dichroic ratio can strengthen the optical property of the device separately that adopts liquid crystal compound of the present invention.
The present invention also relates to a kind of chromatic liquid crystal screen that is used to comprise substrate (liquid crystal compound is the placed thereon or a kind of liquid crystal cells therebetween of colour-LCD), be used to apply electric field electrode, be used for the voltage source that counter electrode provides voltage, and comprise having a kind of liquid crystal compound of the dyestuff of permanent dipole as mentioned above.Certainly, this voltage source can be a kind of external source, also may be for connecting single voltage source as a plurality of unit in display screen.
To explanation already above the advantage of this liquid crystal cells that is used for LCD, especially short to the time of response.
Preferred this substrate is by glass and/or plastic production, and electrode obtains by conductive coating on the substrate.
Preferably a kind of ITO coating of this coating (indium-tin oxide coatings), wherein this coating is coated in glass one side of plastic usually.
The liquid crystal compound film of liquid crystal mixture film between liner plate, especially polymkeric substance disperse, preferred thickness are between 5-40 μ m, and especially preferably between 10-25 μ m, wherein thickness is along the function direction detection, as mentioned above.
Should be noted that the term liner plate not only comprises smooth plate but also comprises the unitary substrat structure of formation of any kind, and comprise this liquid crystal compound in the unit.For this reason, this liner plate or simple substrate comprise the situation that comprises described liquid crystal compound utensil that is useful on.
The invention still further relates in addition to use and be with dipolar dyestuff, preferred permanent dipole liquid crystal cells and/or LCD, as mentioned above.Also as explanation already, the most suitable and preferred liquid crystal cells that is used for LCD is antiparallel birefringent elements, TN-effect unit, PDLC unit and guest-main unit (GH unit).
Must understand, above illustrated and can be used for according to liquid crystal compound of the present invention, and especially with all characteristics of dipolar dyestuff, use with the present invention all also that described to have dipolar dyestuff relevant.
Hereinafter with reference to accompanying drawing These characteristics of the present invention and advantage are further illustrated in detail:
Description of drawings
Fig. 1 signal shows first embodiment of liquid crystal cells of the present invention;
Fig. 2 a, b signal shows that a kind of second embodiment of liquid crystal cells is in the sketch that is connected of connection and off-state with it;
Fig. 3 shows that its rise time (second) is to the graph of a relation of driving voltage frequency (hertz) to having the PDLC unit of different Mo rpip concentration parameter;
Fig. 4 shows according to rise time of Fig. 3 graph of a relation to Morpip concentration;
Fig. 5 is the liquid crystal cells that shows the antiparallel orientations with different Mo rpip concentration parameter, and its rise time (second) is to the graph of a relation of driving voltage frequency (hertz);
Fig. 6 shows according to rise time of Fig. 5 graph of a relation to Morpip concentration;
Fig. 7 shows the graph of a relation of PDLC unit turn-off time (die-away time) to Morpip concentration;
Fig. 8 shows the graph of a relation of a kind of turn-off time (die-away time) of liquid crystal cells of antiparallel orientations to Morpip concentration.
Reference number synopsis among the figure
100 liquid crystal cells
110 substrates
114 conductive coatings
116 polarisation filters
120 liquid crystal compounds
200 liquid crystal cells
210 liner plates
214 conductive coatings
220 liquid crystal compounds
222 liquid crystal droplets
224 polymeric matrixs
230 voltage sources
232 switches
300 screens
310 wires
Fig. 1 signal shows the structure of liquid crystal cells 100.This liquid crystal cells 100 comprises two glass substrate 110, and this two substrates inboard all scribbles ITO (tin indium oxide) coating 114.This element comprises a kind of liquid crystal compound 120, comprises in this liquid crystal compound that 4 '-n-pentyl-4-cyanobiphenyl (5CB) is the dyestuff of the Morpip conduct of 15 ± 1 debye as liquid crystal material and electric dipole moment.This liquid crystal compound 120 comprises the Morpip of 1.0 weight %.
Fig. 2 a, the b signal shows second embodiment of liquid crystal cells 200 of the present invention, and this liquid crystal cells 200 comprises plastic 210, and its inboard only is coated with ITO top coat 214.In this preferred embodiment, liquid crystal compound 220 is a kind of PDLC films, comprises the liquid crystal droplet of even dispersion in transparent polymer matrix 224 in it.This film thickness is 15 μ m, and wherein thickness is measured by described first direction, and this direction is to measure light transmissive preferred or basic orientation and the function of liquid crystal cells also is absolutely necessary.This direction also can be designated as the function direction.
The embodiment that Fig. 2 b explanation is identical as Fig. 2 a, but it is in the state that the ITO top coat 214 of liquid crystal cells 200 is applied voltage.Can find out that from the figure right side applying voltage when enough, be 75 volts this moment, the guiding dipole of each single drop is by being orientated.The specific refractory power of liquid crystal now approaches the specific refractory power of polymer matrix material in the drop, and (this moment, its difference Δ n was lower than 0.002) and this liquid crystal compound become transparent in preferred orientations.By the wiring scheme in Fig. 2 b left side, illustrate to show to have the screen 300 that transfer lever wherein shows specifying information, this point has been described.
Fig. 3-6 explanation is to time of response determination test result's figure.Measure rise time and die-away time, in order to shown according in the liquid crystal material of the present invention with the effect of dipolar dyestuff.Mensuration for the rise time applies driving voltage, wherein sets to apply voltage and can cause 90% the transmission that is transmitted as on-state in preferred orientations, at this moment applies voltage and is set at 25v/15 μ m.Be determined under 24 ± 1 ℃ of the room temperatures and carry out.
Fig. 3 illustrates three kinds of liquid crystal compounds (PDLC mixture that the mixture BL001 of above-mentioned liquid crystal is arranged, provide by Merck Ltd.England company) the result, a liquid crystal compound does not add dyestuff, second Morpip that 0.5 weight % is arranged, the 3rd Morpip that 1.0 weight % are arranged, therefore, second and third belongs to according to liquid crystal compound of the present invention.As the complete determination by driving voltage frequency (500Hz-42kHz) as can be seen, add Morpip 0.5 weight % and 1.0 weight % according to the present invention after, the rise time reduces significantly.Although measuring error is big, as shown in Fig. 3, because only among a small circle variation of temperature, the rise time is with regard to noticeable change, according to this reduction trend of rise time of liquid crystal compound of the present invention, with simple liquid crystal material by comparison, can see clearlyer.Do not compare with not adding with the liquid crystal material of dipolar dyestuff according to prior art, liquid crystal material responses of the present invention gets faster many.
Fig. 4 shows in whole driving voltage range of frequency the mean value by measurement result shown in Figure 3.This figure also illustrates, liquid crystal material is being added Morpip as after having the dyestuff of high permanent dipole moment, and the rise time reduces significantly.
Fig. 5 and 6 has shown same measurement result, but is not according to PDLC mixture of the present invention, but measures comprising according to the antiparallel orientations unit of 5CB liquid crystal material of the present invention.Comprise 0.5 weight % respectively to a kind of liquid crystal material of not having dyestuff according to prior art with according to three of liquid crystal compounds of the present invention, the liquid crystal material of the Morpip of 1.0 weight % and 1.5 weight % has been measured its rise time.
Brilliant material has been measured its rise time.
Fig. 5 and 6 clearlys show, adds the dyestuff that has high electric dipole moment according to the present invention, and the rise time can significantly reduce.
Fig. 7 is the liquid crystal compound that shows according to the embodiment of measuring in Fig. 3 and 4, i.e. dichroism PDLC mixture is to the measurement result figure of turn-off time.This figure shows, adds the Morpip of 0.5 weight %, and almost do not change turn-off time.But add the Morpip of 1.0 weight %, slightly increase die-away time.It is higher to mix concentration, and die-away time is slightly long, is likely because due to the viscosity increase of liquid crystal display.
Fig. 8 show as shown in Figure 7 to the unitary same measured result of antiparallel orientations, this be shown in Fig. 5 and 6 in to record the result relevant.Although also expect in this case since viscosity increase die-away time can be longer, even beat all be the Morpip that finds to adopt greater concn 2.0 weight %, its die-away time is almost constant.
The above results clearlys show shown in Fig. 3 to 8, and liquid crystal compound of the present invention can significantly reduce the rise time of liquid crystal cells, and this quality to liquid crystal display is extremely important, as mentioned above.On the other hand, added the influence that has dipolar dyestuff this die-away time hardly.Must remember that certainly when interpolation does not have the dyestuff of moment of dipole, because the viscosity of the liquid crystal compound of above explanation increases, also can increase this die-away time.
Embodiment
About manufacture method, now will produce an embodiment who comprises the steps in the preferred embodiment of PDLC unit (or TN unit) and be described in down according to liquid crystal cells of the present invention:
1, the preparation of glass unit.Element thickness is measured and is adopted HP 4278A 1kHz/1MHz capacity meter (Hewlett-Packard's product) to carry out.At 21 ℃ of electric capacity of measuring empty glass unit down of room temperature, calculate its thickness then.Used these unit are ready-made empty glass sandwich unit, are provided by Japanese E.H.C.Ltd company.Their both sides precoating ITO.Adopt 15 μ m not have the unit of orientation to make the PDLC unit.Select for use the unit of the antiparallel orientations of 5 μ m to make birefringent lc unit.
2, the preparation of dichroic dye.Dyestuff obtains by recrystallize, so the purity height.They are remained in 80 ℃ of vacuum drying ovens the above time in a week, to get rid of since water in air gas the ionic impurity that may cause.
3, the preparation of dichroism PDLC mixture.The UV curable polymer (NOA65) of getting 0.05 milliliter mixes with 0.05 milliliter liquid crystal (BL001), obtains 44.3 weight %BL001 mixtures.
4, blending guest dyestuff in the liquid crystal.In liquid crystal compound, add an amount of dyestuff (Morpip), obtain the mixture of required dye strength.Then, it is positioned in the dark to stir spends the night, see photodegradation to avoid dyestuff.Filter this mixture (high pressure liquid chromatography (HPLC) method (HPLC Acrodisc 0.45 μ m)) then,,, even may become the reason that causes grit because liquid crystal distortion institute energy requirement is very little to remove any undissolved crystal grain.
5, filling liquid crystal mixture in glass unit.Sample adopts the suitable empty glass unit manufacturing of measuring through 1.Add several mixtures to unitary opening end, utilize capillary force to load these unit.Then these unit were positioned in the vacuum drying oven any bubble of removing in the unit to be comprised 15 minutes.Vacuum drying oven remains on 80 ℃ and (just in time is higher than T
N-ITo BL001 is 61 ℃, is 35 ℃ to 5CB), to get rid of the defective of the possible flow orientation that causes when the wicking action gravitational attraction mixture.Use two opening ends of Resins, epoxy closed cell then, prevent owing to may polluting that outside air causes.
6, initiation is separated, and forms PDLC.Shone 2 minutes down at 21 ℃ with UV-light (Spectroline, ModelEN-180 L/F, 230V, 50Hz, 0.17A=39.1W, use under 110 millimeters), polymeric blends is fully solidified.Liquid crystal droplet after being separated with the cruciform polarized light microscope observing, the diameter of observing them is several μ m.
When producing the TN unit and replace the PDLC unit, mix and be with dipolar dyestuff, make the 5CB birefringence liquid crystal, the Morpip in preferred embodiment is as the guest in the liquid crystal, in this preferred embodiment 4 '-n-pentyl-4-cyanobiphenyl (5CB) is as main.Can omit the unitary above-mentioned steps 3 of production dichroism PDLC and 6 in this case.
In this specification sheets, claims and/or accompanying drawing disclosed characteristics of the present invention can be separately and its arbitrary combination realize material of the present invention with various forms.
Claims (47)
1, a kind of liquid crystal compound, it comprises a kind of liquid crystal material and a kind of dyestuff, it is characterized in that described dyestuff has a kind of dipole, wherein said liquid crystal compound is used for the liquid crystal cells of chromatic liquid crystal screen, and the order parameter S of described liquid crystal compound is at least 0.5, and described order parameter S is defined as:
A wherein
‖And A
⊥Be respectively to the absorbance determination value under unit disconnection and the on-state.
2,, it is characterized in that described liquid crystal material has a kind of permanent dipole according to the liquid crystal compound of claim 1.
3,, it is characterized in that described liquid crystal material has a kind of induced dipole according to the liquid crystal compound of claim 1.
4,, it is characterized in that described liquid crystal material has ferroelectric properties according to the liquid crystal compound of claim 1.
5,, it is characterized in that described liquid crystal compound resistivity is greater than 10 according to the liquid crystal compound of claim 1
12Ω cm.
6,, it is characterized in that described liquid crystal compound resistivity is greater than 10 according to the liquid crystal compound of claim 5
13Ω cm.
7,, it is characterized in that described liquid crystal material is a kind of liquid crystal blending thing according to the liquid crystal compound of claim 1.
8,, but it is characterized in that described liquid crystal compound is the electric field conversion and is orientated by surface effects according to the liquid crystal compound of claim 1.
9, according to each liquid crystal compound among the claim 1-8, it is characterized in that described liquid crystal material be 4 '-n-pentyl-4-cyanobiphenyl, show with the following formula structural table:
10, according to each liquid crystal compound among claims 1-8, it is characterized in that described liquid crystal compound comprises the liquid crystal droplet that is scattered in the transparent polymer matrix.
11,, it is characterized in that described polymeric matrix comprises a kind of polymkeric substance of radiation-curable or thermofixation according to the liquid crystal compound of claim 10.
12,, it is characterized in that described liquid crystal compound forms by mixing according to the liquid crystal compound of claim 8.
13, according to the liquid crystal compound of this claim 8, it is characterized in that the specific refractory power of the polymkeric substance of described polymeric matrix, when liquid crystal droplet by when applying electric field orientation, approach specific refractory power in first direction liquid crystal droplet (222).
14, according to each liquid crystal compound among the claim 1-8, it is characterized in that described liquid crystal compound is exercisable in guest-main unit.
15,, it is characterized in that described dyestuff has a kind of permanent dipole of at least 5 debye according to the liquid crystal compound of claim 14.
16,, it is characterized in that described dyestuff has a kind of permanent dipole of at least 10 debye according to the liquid crystal compound of claim 15.
17,, it is characterized in that described dyestuff has a kind of permanent dipole of at least 15 debye at least according to the liquid crystal compound of claim 15.
18,, it is characterized in that described liquid crystal compound order parameter S is at least 0.7 according to the liquid crystal compound of claim 1.
19, according to each liquid crystal compound among the claim 1-8, it is characterized in that the solubleness of described dyestuff is at least 0.5 weight % in whole liquid crystal compound.
20,, it is characterized in that the solubleness of described dyestuff is at least 1 weight % in whole liquid crystal compound according to the liquid crystal compound of claim 19.
21,, it is characterized in that described dyestuff is with following chemical formulation according to each liquid crystal compound among the claim 1-8:
22,, it is characterized in that described dyestuff is with following chemical formulation according to each liquid crystal compound among the claim 1-8:
Wherein D represents electron donor's group, and π represents that pi-conjugated system and A represent that electronics is subjected to main group.
23,, it is characterized in that D is selected from dialkyl amido, pyrido and/or Mi Dingbing according to the liquid crystal compound of claim 22.
24,, it is characterized in that π is selected from thiphene ring unit, phenyl unit and/or vinyl units according to the liquid crystal compound of claim 22.
25,, it is characterized in that A is selected from nitro, dicyano methanides and/or tricyanomethanides according to the liquid crystal compound of claim 22.
26, be used for the liquid crystal cells of chromatic liquid crystal screen, it comprises:
-a kind of liquid crystal compound (120,220)
-be used to comprise the liner plate (110,210) of described liquid crystal compound (120,220),
-be used for described liquid crystal compound (120,220) is applied the electrode (112,114) of electric field,
-being used for described electrode (110,210) is applied a kind of voltage source (230) of voltage, wherein said liquid crystal compound (120,220) comprises a kind of dyestuff,
It is characterized in that
Described dyestuff has a kind of dipole,
The order parameter S of described liquid crystal compound is at least 0.5, and described order parameter S is defined as:
A wherein
‖And A
⊥Be respectively to the absorbance determination value under unit disconnection and the on-state.
27,, it is characterized in that liquid crystal compound is according to each a kind of mixture among the claim 1-25 according to the liquid crystal cells of claim 26.
28,, it is characterized in that described liner plate (110,210) is to be made by glass and/or plastics according to the liquid crystal cells of claim 26.
29,, it is characterized in that described electrode is that coating by liner plate (110,210) provides according to the liquid crystal cells of claim 26.
30,, it is characterized in that described coating is a kind of ITO coating (112,114 according to the liquid crystal cells of claim 29; 214).
31,, it is characterized in that described ITO coating (114) is the two sides that are coated in liner plate (110) according to the liquid crystal cells of claim 30.
32, according to each liquid crystal cells among the claim 26-31, it is characterized in that described liquid crystal compound (120,220) fills between the described liner plate, the thickness of wherein said layer is 5-40 μ m at described first direction.
33,, it is characterized in that the thickness of wherein said layer is 10-25 μ m at described first direction according to the liquid crystal cells of claim 32.
34, has the application that dipolar dyestuff is used for liquid crystal compound.
35, according to the application of the dyestuff of claim 34, it is characterized in that described liquid crystal compound is contained in liquid crystal cells and/or the liquid crystal display.
36, according to the application of the dyestuff of claim 35, it is characterized in that described liquid crystal cells is a kind of liquid crystal cells of antiparallel orientations.
37, according to the application of the dyestuff of claim 35, it is characterized in that described liquid crystal cells is a kind of PDLC unit.
38, according to the application of the dyestuff of claim 35, it is characterized in that described liquid crystal cells is a kind of GH unit.
39, according to the application of the dyestuff of claim 34, it is characterized in that described dyestuff has permanent dipole.
40, according to the application of the dyestuff of claim 39, it is characterized in that described dyestuff has the permanent dipole of at least 5 debye.
41, according to the application of the dyestuff of claim 40, it is characterized in that described dyestuff has the permanent dipole of at least 10 debye.
42, according to the application of the dyestuff of claim 40, it is characterized in that described dyestuff has the permanent dipole of at least 15 debye.
43,, it is characterized in that described dyestuff is with following chemical formulation according to the application of each dyestuff among the claim 34-42:
44,, it is characterized in that described dyestuff is to represent with following formula according to the application of each dyestuff among the claim 34-42:
Wherein D represents a kind of electron donor's group, and π represents that a kind of pi-conjugated system and A represent that a kind of electronics is subjected to main group.
45, according to the application of the dyestuff of claim 44, it is characterized in that D is selected from dialkyl amido, pyrido, Mi Dingbing.
46, according to the application of the dyestuff of claim 44, it is characterized in that π is selected from thiphene ring unit, phenyl unit, vinyl units.
47, according to the application of the dyestuff of claim 44, it is characterized in that A is selected from nitro, dicyano methanides and/or tricyanomethanides.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP00122028.4 | 2000-10-10 | ||
| EP00122028 | 2000-10-10 | ||
| EP01110255A EP1197791A3 (en) | 2000-10-10 | 2001-04-25 | Liquid crystal mixture including a dye with a dipole |
| EP01110255.5 | 2001-04-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1346866A CN1346866A (en) | 2002-05-01 |
| CN1234801C true CN1234801C (en) | 2006-01-04 |
Family
ID=26071492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011354046A Expired - Fee Related CN1234801C (en) | 2000-10-10 | 2001-10-10 | Liquid crystal mixture and liquid crystal unit and use of dye having dipole for mixture |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6737126B2 (en) |
| EP (1) | EP1197791A3 (en) |
| JP (1) | JP4394317B2 (en) |
| CN (1) | CN1234801C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60221671T2 (en) * | 2002-10-23 | 2008-04-30 | Sony Deutschland Gmbh | Negative type liquid crystals containing dopants |
| EP1541661B1 (en) * | 2003-12-11 | 2008-04-02 | Sony Deutschland GmbH | A composition comprising a liquid crystal material and an additive |
| TWI428053B (en) | 2004-02-09 | 2014-02-21 | Idemitsu Kosan Co | Organic electroluminescent element |
| JP4964123B2 (en) * | 2004-04-16 | 2012-06-27 | ディ．ケイ． アンド イー．エル． マクフェイル エンタープライジーズ プロプライエタリー リミテッド | Method of forming an optically active device used as a tunable photonic crystal with a cavity structure |
| EP1840188B1 (en) | 2006-03-31 | 2011-09-07 | Sony Deutschland GmbH | A composition comprising at least one type of liquid crystal |
| KR20120125859A (en) * | 2011-05-09 | 2012-11-19 | 삼성디스플레이 주식회사 | Liquid crystal display device and method of manufacturing a liquid crystal display device |
| CN102516163B (en) * | 2011-12-02 | 2013-09-25 | 江苏德威新材料股份有限公司 | Preparation and application of liquid crystal functionalized pyridine compound |
| CN102901047B (en) * | 2012-10-13 | 2014-11-05 | 江苏和成显示科技股份有限公司 | Photodiffusion film, backlight module and liquid crystal display with photodiffusion film |
| SG11201602964XA (en) * | 2013-11-06 | 2016-05-30 | Univ Singapore | Electrochromic device with graphene/ferroelectric electrode |
| CN105824145B (en) * | 2015-01-08 | 2019-06-04 | 江苏和成显示科技有限公司 | Liquid crystal display device and its driving method |
| WO2018068237A1 (en) * | 2016-10-12 | 2018-04-19 | 清华大学 | Liquid crystal droplet and preparation method, biosensor and method for detecting biological sample |
| EP3561558A4 (en) * | 2016-12-23 | 2020-01-22 | LG Chem, Ltd. | Variable reflectivity mirror |
| US11249365B2 (en) | 2019-09-05 | 2022-02-15 | Facebook Technologies, Llc | Magnetic field driven liquid crystal patterning control system |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3666881A (en) * | 1970-12-28 | 1972-05-30 | Richard J Stein | Electro-optical display device employing liquid crystals |
| US3983049A (en) * | 1974-05-02 | 1976-09-28 | General Electric Company | Liquid crystal compositions with positive dielectric anisotropy |
| JPS58103578A (en) * | 1981-12-16 | 1983-06-20 | Alps Electric Co Ltd | Color liquid crystal display element |
| JP2636271B2 (en) * | 1987-10-30 | 1997-07-30 | ソニー株式会社 | Manufacturing method of ferroelectric liquid crystal |
| DE69118261T2 (en) * | 1990-07-20 | 1996-12-05 | Mitsubishi Rayon Co | Compound containing optically active delta-valerolactone ring and liquid-crystalline composition containing the same |
| US5744267A (en) * | 1994-10-12 | 1998-04-28 | Arizona Board Of Regents Acting For And On Behalf Of University Of Arizona | Azo-dye-doped photorefractive polymer composites for holographic testing and image processing |
-
2001
- 2001-04-25 EP EP01110255A patent/EP1197791A3/en not_active Withdrawn
- 2001-10-09 US US09/973,407 patent/US6737126B2/en not_active Expired - Fee Related
- 2001-10-10 JP JP2001313179A patent/JP4394317B2/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2002194357A (en) | 2002-07-10 |
| EP1197791A2 (en) | 2002-04-17 |
| US6737126B2 (en) | 2004-05-18 |
| CN1346866A (en) | 2002-05-01 |
| EP1197791A3 (en) | 2002-12-04 |
| JP4394317B2 (en) | 2010-01-06 |
| US20020084442A1 (en) | 2002-07-04 |
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